KR102399700B1 - Aerogel composite and fabricating method of the same - Google Patents

Abstract

The present invention relates to a method for manufacturing an airgel composite with improved thermal insulation and processability, and to an airgel composite prepared thereby. The method of manufacturing an airgel composite according to an embodiment of the present invention includes: a) providing an airgel having a plurality of pores; b) heating the airgel, modifying the surface of the airgel to be hydrophilic; c ) Filling the pores with the liquid by immersing the hydrophilic modified airgel in a hydrophilic liquid, d) the airgel or the airgel surface in which the pores are filled with the liquid Reacting the hydrophilic liquid with an isocyanate-based compound, It may include coating the surface of the airgel with polyurea.

Description

Airgel composite and its manufacturing method {Aerogel composite and fabricating method of the same}

The present invention relates to a method for coating an airgel using polyurea. Additionally, the present invention relates to a method for preparing a polyurea-coated airgel and its use, and to a method capable of manufacturing a highly insulating airgel-polyurethane composite foam using the polyurea-coated airgel.

Polyurethane foam, which is used as an insulating material in various fields due to its light weight, specific strength and thermal insulation performance, is required to have improved thermal insulation performance to reduce energy loss. In order to improve the insulation performance of polyurethane foam, a method that can minimize conduction, convection, and radiant energy based on the heat transfer mechanism occurring within the foam must be applied. As a method for this, recently silica airgel-polyurethane composite foam using silica airgel is also used.

The nano-sized pores constituting the silica airgel are formed with a diameter of 50 nm or less, which is shorter than the wavelength of radiation (>700 nm) and the gas mean free movement path (70 nm). teeth are minimized. For this reason, silica airgel is known as a material that exhibits very high thermal insulation performance (0.01 to 0.03 W/mK). However, silica airgel has limited application as an insulator due to its low mechanical properties and limitations in processability due to its powder-type manufacturing method.

Accordingly, in order to supplement the strength and durability of silica airgel and to increase processability, research on the development of a silica airgel-organic polymer composite is being conducted. In particular, when a composite is synthesized by adding silica airgel to a polymer matrix, it is expected that the thermal insulation performance of the matrix can be improved due to the low thermal conductivity of the silica airgel, and research on the composite is attracting more attention.

However, when the silica airgel-polymer composite is prepared, the polymer resin penetrates into the pores of the silica airgel and loses the nanopore properties of the silica airgel, resulting in that the thermal insulation properties of the composite cannot be improved. In particular, when silica airgel is applied to polyurethane foam to prepare a silica airgel-polyurethane composite foam, the pore properties of the silica airgel disappear due to pore penetration of the polymer resin, as well as the low between organic polyurethane and inorganic silica. There was a problem that the thermal insulation performance was lowered than that of the conventional polyurethane foam due to the decrease in mechanical strength due to the bonding force and the increase or collapse of the pore size of the polyurethane foam.

Laid-open Patent Publication No. 10-2015-0045160

The problem to be solved by the present invention is to prevent the pore penetration of the polymer resin occurring in the process of manufacturing the airgel-polyurethane composite foam, and to improve the thermal insulation performance of the composite foam by using polyurea prior to manufacturing the composite foam. It relates to a method of coating the airgel.

More specifically, the hydrophobic airgel is heat-treated at a high temperature to be modified to be hydrophilic, and the hydrophilic airgel is mixed with a hydrophilic liquid (eg, water) and mixed with an isocyanate-based compound. Because the liquid is filled, the isocyanate-based compound with low miscibility with the hydrophilic liquid does not penetrate into the pores, and reacts with the hydrophilic liquid on the airgel surface to produce polyurea. In the drying step, the liquid inside the pores is removed, and the airgel composite can be obtained that maintains the pores of the airgel and has a surface coated with polyurea. Using this, it is also an object to form a polyurethane foam excellent in thermal insulation and mechanical properties.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention, claims and drawings.

The method of manufacturing an airgel composite according to an embodiment of the present invention for achieving the above-described problem, a) providing an airgel having a plurality of pores formed therein, and b) heating the airgel, the surface of the airgel hydrophilic modification; c) immersing the hydrophilically modified airgel in a hydrophilic liquid to fill the pores with the liquid; d) the airgel or the hydrophilic liquid on the surface of the airgel in which the pores are filled with the liquid and reacting the isocyanate-based compound, and coating the surface of the airgel with polyurea.

Step b) may be performed in a temperature atmosphere of 300°C to 500°C.

After step d), the method may further include drying the airgel in a temperature atmosphere of 120° C. to 200° C. for 48 hours to 72 hours.

The liquid filled in the pores may be removed.

The airgel may be formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide.

The isocyanate-based compound is polymeric methylene diphenyl diisocyanate (PMDI), monomer methylene diphenyl diisocyanate (MMDI), toluene diisocyanate, torilene diisocyanate (torilene) diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI).

The hydrophilic liquid may include water, methanol, ethanol, isopropanol, diol, triol, diamine, triamine, or a mixture of two or more thereof.

The airgel composite according to another embodiment of the present invention for achieving the above object may include an airgel having a plurality of pores and a polyurea coated on the surface of the airgel.

The polyurea is characterized in that it is not coated on the pores of the airgel.

The airgel may be formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide.

A polyurethane foam composition with improved thermal insulation performance according to another embodiment of the present invention for achieving the above object is a polyol mixture, an isocyanate-based compound, an airgel having a plurality of pores, and coating the surface of the airgel It may include an airgel composite composed of polyurea.

The polyurea is characterized in that it is not coated on the pores of the airgel.

The polyol mixture may include a polyether polyol and a polyester polyol.

In the polyol mixture, a mixing ratio of the polyether polyol and the polyester polyol is 5:5 to 7:3.

The polyether polyol is polyethylene glycol, polypropylene glycol, polyoxypropylenetriol glycol, or plytetramethylene glycol.

The polyester polyol is diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1 ,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 ,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-n- At least one selected from the group consisting of butyl-2-ethyl-1,3-propanediol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naphthylene dicarboxylic acid .

The isocyanate-based compound is, polymeric methylene diphenyl diisocyanate (PMDI), monomer methylene diphenyl diisocyanate (monomer methylene diphenyl diisocyanate, MMDI), toluene diisocyanate (toluene diisocyanate), torylene diisocyanate ( torilene diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI), and hexamethylene diisocyanate (HMDI).

The airgel may be formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide.

A blowing agent is further included, wherein the blowing agent is water, cyclopentane, carbon dioxide, hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroolefin (HFO) or methane dichloride. .

It may further include an additive.

The additive is at least one selected from the group consisting of a foaming catalyst, a gelling catalyst, and a surfactant.

A polyurethane foam according to another embodiment of the present invention for achieving the above object includes a cured product of the polyurethane foam composition.

According to the present invention, in order to prevent pore penetration of the polymer resin occurring in the process of manufacturing the airgel-polyurethane composite foam, and to improve the thermal insulation performance of the composite foam, polyurea is used prior to manufacturing the composite foam. A method of coating an airgel is provided. In addition, a polyurethane foam excellent in thermal insulation and mechanical strength is provided based on the airgel composite prepared thereby.

1 shows a manufacturing process of an airgel composite according to an embodiment of the present invention.
2 is a flowchart showing a method of manufacturing an airgel composite according to an embodiment of the present invention.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the technical field to which the present invention belongs It is provided to fully inform the possessor of the scope of the invention, and the present invention is only defined by the scope of the claims. With reference to the accompanying drawings will be described in detail for the implementation of the present invention. Irrespective of the drawings, like reference numbers refer to like elements, and "and/or" includes each and every combination of one or more of the recited items.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, “comprises” and/or “comprising” does not exclude the presence or addition of one or more other components in addition to the stated components.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

Hereinafter, a method for manufacturing an airgel composite according to embodiments of the present invention, an airgel composite, and a polyurethane foam composition including the same will be described.

Figure 1 shows the manufacturing process of the airgel composite according to an embodiment of the present invention, Figure 2 is a flowchart showing the manufacturing method of the airgel composite according to an embodiment of the present invention. With reference to FIGS. 1 and 2 , a method for manufacturing an airgel composite and an airgel composite according to an embodiment of the present invention will be described as follows.

The method of manufacturing an airgel composite according to an embodiment of the present invention includes: a) providing an airgel having a plurality of pores; b) heating the airgel, modifying the surface of the airgel to be hydrophilic; c ) Filling the pores with the liquid by immersing the hydrophilic modified airgel in a hydrophilic liquid, d) the airgel or the airgel surface in which the pores are filled with the liquid Reacting the hydrophilic liquid with an isocyanate-based compound, It may include coating the surface of the airgel with polyurea.

First, an airgel 10 having a plurality of pores is provided (S10). The airgel 10 having a plurality of pores may be formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide, and tin oxide. In a preferred embodiment, the airgel may be formed of silica. Hereinafter, for convenience of description, unless otherwise specified, it is assumed that the airgel of the present invention is formed of silica.

On the other hand, if the diameter of the pores formed in the airgel 10 may have a size of 1 to 100 nm, the pores may be formed in the form of a plurality of passages connecting the inside and outside of the airgel 10 .

Subsequently, the airgel 10 is heated to modify the surface of the airgel 10 (S20). More specifically, the surface of the provided airgel 10 may have a hydrophobic property (11). It is to convert the surface of the airgel 10, which is a property of hydrophobicity (11), into hydrophilicity (12) through a modification process. The reforming process may be performed by applying heat to the airgel 10 . That is, the airgel 10 is heated in a temperature atmosphere of 300 ℃ to 500 ℃. The surface of the airgel 10 is modified from hydrophobicity 11 to hydrophilicity 120 by heat. Thereby, the polar or hydrophilic material and the surface of the airgel 10 may react.

Subsequently, the airgel 10 whose surface is modified to be hydrophilic 12 is immersed in the hydrophilic liquid, and the pores are filled with the liquid (S30). The hydrophilic liquid may include water, methanol, ethanol, isopropanol, diol, triol, diamine, triamine, or a mixture of two or more thereof. In a preferred embodiment, the hydrophilic liquid may be water.

Subsequently, an isocyanate-based compound is added to the hydrophilic liquid in which the airgel 10 is immersed. Thereby, the airgel with pores filled with the liquid reacts with the isocyanate-based compound to coat the surface of the airgel with polyurea (S40). Alternatively, the surface of the airgel is coated with polyurea by reacting the hydrophilic liquid on the surface of the airgel with an isocyanate-based compound (S40).

The hydroxyl group of the hydrophilic liquid and the isocyanate group of the isocyanate-based compound may react to form the polyurea 20 . On the other hand, it is difficult for the isocyanate-based compound to penetrate into the pores by the liquid filled in the pores, so that the polyurea 20 may be formed only on the surface of the airgel 10 . That is, the polyurea 20 is not coated on the pores of the airgel 10 .

Therefore, when the polyurethane foam is formed, the polymer formation reaction occurs only on the surface of the airgel composite 1, and the polymer formation reaction may not proceed in the pores of the airgel composite 1 . That is, the airgel composite 1 of the present invention has a characteristic that can retain reactivity and heat insulation at the same time. The airgel composite (1) of the present invention does not penetrate the pores of the polymer resin or the like during the manufacturing process, so it is possible to maintain the inherent thermal insulation properties of the airgel.

Here, the isocyanate-based compound is a polymeric methylene diphenyl diisocyanate (PMDI), a monomer methylene diphenyl diisocyanate (monomer methylene diphenyl diisocyanate, MMDI), toluene diisocyanate (toluene diisocyanate), torylene diisocyanate (torilene diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI), and may be any one selected from the group consisting of hexamethylene diisocyanate (HMDI).

Subsequently, after coating the surface of the airgel with polyurea, a step of drying the airgel in a temperature atmosphere of 120°C to 200°C for 48 hours to 72 hours is performed. Thereby, the liquid filled in the pores can be removed.

If the drying temperature is less than 120 °C, evaporation of the liquid filled in the pores may not be smooth. On the other hand, if the drying temperature exceeds 200 ℃, the surface properties of the airgel, polyurea, etc. may cause thermal denaturation, which may be undesirable. If the drying time is less than 48 hours, liquid may remain in the pores and pore passages, and if it exceeds 72 hours, the processing time may increase unnecessarily.

When the liquid filled in the pores of the airgel is removed through the drying process, finally, the airgel 10 in which a plurality of pores are formed, and the airgel composite (1) comprising a polyurea 20 coated only on the surface of the airgel is formed (S50).

In the manufacture of the airgel composite, the content of the component included in the composition for the airgel composite to be formed is as follows.

The composition for the airgel composite may include 10-15% by weight of the airgel, 40-60% by weight of the hydrophilic liquid, and 20-30% by weight of the isocyanate-based compound, based on the total weight of the composition for the airgel composite.

If the content of the airgel is less than 10% by weight, the amount of the composite to be formed is not sufficient, and if it exceeds 15% by weight, it may be difficult to form a high-quality composite. If the content of the hydrophilic liquid is less than 40% by weight, it is insufficient to fill the pores and form a polyurea, and if it exceeds 60% by weight, it is difficult to exert an effect relative to the amount added. When the content of the isocyanate-based compound is less than 20% by weight, the formation of polyurea on the airgel surface is insufficient, and when it exceeds 30% by weight, the residual amount of the unreacted isocyanate-based compound may increase.

Next, a polyurethane foam composition according to another embodiment of the present invention will be described.

The polyurethane foam composition with improved thermal insulation according to an embodiment of the present invention may include an airgel composite composed of a polyol mixture, an isocyanate-based compound, an airgel having a plurality of pores, and polyurea coating the surface of the airgel. .

The polyurea included in the airgel composite may cause a reaction with an isocyanate-based compound and an allophanate or biuret, and a crosslinking reaction may proceed. In addition, the pores included in the airgel composite may provide thermal insulation to the polyurethane foam.

First, the airgel composite composed of an airgel having a plurality of pores and polyurea coating the surface of the airgel is substantially the same as the airgel composite described above. At this time, polyurea is not coated on the pores of the airgel. The airgel may be formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide, and tin oxide.

The polyol compound may include polyether polyols and polyester polyols.

In the polyol mixture, a mixing ratio of the polyether polyol and the polyester polyol may be 5:5 to 7:3. The content of polyether polyol may be slightly higher than that of polyester. Since polyether polyol has superior hydrolysis resistance and low-temperature characteristics compared to polyester polyol, polyether polyol is used slightly more than polyester polyol. However, since the polyester polyol has excellent heat resistance compared to the polyether polyol, when used outside the above range, the heat resistance of the polyurethane foam to be formed may become weak.

That is, considering the water resistance and heat resistance of the polyurethane foam to be formed of the polyol compound, it will be possible to use a mixture of polyether polyol and polyester polyol within the above range.

Here, the polyester polyol is diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol; 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-n -Butyl-2-ethyl-1,3-propanediol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, at least one selected from the group consisting of oxalic acid and naphthylene dicarboxylic acid can be one

In addition, the polyether polyol may be polyethylene glycol, polypropylene glycol, polyoxypropylenetriol glycol or polytetramethylene glycol.

More specifically, polyether polyols can be prepared by reacting at least one alkylene oxide containing 2 to 4 carbon atoms in an alkylene radical with a starting material containing a hydrogen atom to which two active groups are bonded. Suitable alkylene oxides include ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide, preferably ethylene oxide, propylene oxide and 1,2 - A mixture of propylene oxide and ethylene oxide is good. Examples suitable as starting materials are water, amino alcohols such as N-alkyl-diethanolamine (eg N-methyl-diethanolamine) and diols (eg ethylene glycol, 1,3-propylene glycol, 1 ,4-butanediol and 1,6-hexanediol).

Other suitable polyether diols are polymerization products of tetrahydrofuran containing hydroxyl groups. Trifunctional polyethers in a proportion of 0 to 30% by weight relative to difunctional polyethers can be used, but the maximum amount should be such that a thermoplastically processable product is obtained. These straight-chain polyether polyols may be used alone or in the form of a mixture of two or more.

The isocyanate-based compound is polymeric methylene diphenyl diisocyanate (PMDI), monomer methylene diphenyl diisocyanate (MMDI), toluene diisocyanate, torilene diisocyanate (torilene). diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI), and hexamethylene diisocyanate (HMDI) may be any one selected from the group consisting of.

In general, a polyurethane adhesive composition is prepared by forming a urethane group by chemically reacting with an isocyanate compound having a polyfunctional group and a polyol. Since the isocyanate group (-N=C=O) tends to bond with the hydroxyl group (-OH) very easily (urethane bond), a linear polymer is formed when a polyol having two hydroxyl groups is reacted with diisocyanate. is polyurethane.

The polyurethane foam composition according to the present invention promotes a smooth urethane production reaction with a polyol mixture through an MDI (Methylene Diphenyl Diisocyanate)-based isocyanate compound, so that an excellent elastic effect unique to polyurethane can be realized. The degree of crosslinking and cohesive force of the polyurethane resin composition, which can be excessively increased by reaction with a polyol compound having a high average number of functional groups through an isocyanate-based compound having an isocyanate group (NCO) content % of 30 to 32 can control

On the other hand, the polyurethane foam composition according to an embodiment of the present invention may further include a foaming agent.

The blowing agent may be water, cyclopentane, carbon dioxide, hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroolefin (HFO) or methane dichloride. With the blowing agent, a foamed foam can be formed.

An additive may be further included in the polyurethane foam composition according to an embodiment of the present invention.

The additive may be at least one selected from the group consisting of a foaming catalyst, a gelling catalyst, and a surfactant.

The foaming catalyst may assist the activation of the foaming agent, thereby promoting the formation of foam in the composition. When the foam is formed on the polyurethane resin, the surfactant prevents the resulting foam from being united and destroyed, and serves to adjust the foam to form a uniform foam. As the surfactant, a silicone surfactant may be used.

The gelling catalyst promotes, for example, a reaction between a polyol mixture and an isocyanate-based compound to form a polyurethane resin. The gelling catalyst is triethanolamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpyrrazine, 2-(dimethylamino-ethoxy)-ethanol, diazabicyclo-(2,2,2)- At least one selected from the group consisting of octane, esters of titanic acid, iron compounds, tin diacetate, tin dioctaate, tin dilaurate, dibutyltin dilaurate and dialkyl tin salts of aliphatic carboxylic acids. can be

On the other hand, the polyurethane foam composition may further include a chain extender. The chain extender is used in the chain extension reaction when the polyurethane polymer is formed. Chain extenders include ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, 1,4-butadiol, glycerin, polyethylene glycol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene At least one selected from the group consisting of glycol, dibutylene glycol, 1,3-butyrene glycol, diethanolamine, triethanolamine, 1,5-naphthalenediamine and 4,4'-methylene-bis(2-chloroaniline) can be

The content ratio of the substances included in the polyurethane foam composition is as follows.

Based on the total weight of the polyurethane foam composition, 35-60% by weight of a polyol mixture, 5-15% by weight of an airgel composite, 40-60% by weight of an isocyanate-based compound, 5-20% by weight of a blowing agent, 0.01-2% by weight % of additives may be mixed.

When the content of the polyol mixture and the isocyanate-based compound is less than 35% by weight, it becomes difficult to form a polyurethane foam, and when it exceeds 60% by weight, it is not in harmony with other additives, forming a foam having good thermal insulation performance This can be difficult.

When the content of the airgel composite is less than 5% by weight, the thermal insulation performance by the addition of the airgel composite is not sufficient, and when it exceeds 15% by weight, the mechanical stability of the foam may be reduced.

If the content of the blowing agent is less than 5% by weight, the formation of the foam in the foam is not sufficient, and if it exceeds 20% by weight, the mechanical stability of the foam may be deteriorated. If the content of the additive is less than 0.01% by weight, the effect of the additive does not appear, and if it exceeds 2% by weight, the amount added is excessive compared to the required effect.

A polyurethane foam comprising a cured product obtained by curing the polyurethane foam composition is formed. That is, to form a polyurethane foam from the polyurethane foam composition.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Example 1: Preparation of airgel composite

After heating the silica airgel to a temperature of 500°C, 15% by weight of silica airgel and 60% by weight of water were mixed, and then, 25% by weight of polymeric methylene diphenyl diisocyanate as an isocyanate-based compound (polymeric methylene diphenyl diisocyanate, PMDI) was mixed. Thereafter, after drying by heating at a temperature of 120° C. for 48 hours, a silica airgel composite coated with polyurea was obtained.

Example 2: Preparation of polyurethane foam comprising airgel composite

1 wt% of surfactant and 5 wt% of a blowing agent (HFO-1233zd), 0.1 wt% of a foaming catalyst (N,N,N) in 40 wt% of a polyol mixture (polyether polyol: polyester polyol = 6:4) ',N",N"-pentamethyldiethylenetriamine), gelling catalyst (33% triethylenediamine + 67% dipropylene glycol), and 6% by weight silica airgel coated with polyurea, 47.8% by weight of polymeric methylenediamine A silica airgel-polyurethane foam was prepared by mixing phenyl diisocyanate (polymeric methylene diphenyl diisocyanate, PMDI). The density of the polyurethane foam prepared in this example was 90.8 kg/m 3 , the thermal conductivity was 0.0215 W/mK, and the compressive strength was 1.18 MPa.

Example 3: Preparation of polyurethane foam comprising airgel composite

37% by weight of polyol mixture (polyether polyol: polyester polyol = 6:4), 1% by weight of surfactant and 6% by weight of blowing agent (HFO-1233zd), 0.1% by weight of foaming catalyst (N,N,N) ',N",N"-pentamethyldiethylenetriamine), gelling catalyst (33% triethylenediamine + 67% dipropylene glycol), and 12 wt% silica airgel coated with polyurea, 43.8 wt% polymeric methylene diamine A silica airgel-polyurethane foam was prepared by mixing phenyl diisocyanate (polymeric methylene diphenyl diisocyanate, PMDI). The density of the polyurethane foam prepared in this example was 90.1 kg/m 3 , the thermal conductivity was 0.0207 W/mK, and the compressive strength was 1.19 MPa.

Comparative Example: Polyurethane foam production without airgel composite

1 wt% of surfactant and 4.2 wt% of a blowing agent (HFO-1233zd), 0.1 wt% of a foaming catalyst (N,N,N) in 43 wt% of a polyol mixture (polyether polyol: polyester polyol = 6:4) ',N",N"-pentamethyldiethylenetriamine), gelling catalyst (33% triethylenediamine + 67% dipropylene glycol), and 51.6% by weight polymeric methylene diphenyl diisocyanate (PMDI) were mixed to form silica Airgel-polyurethane foam was prepared. The density of the polyurethane foam prepared in this example was 90.5 kg/m 3 , the thermal conductivity was 0.02223 W/mK, and the compressive strength was 1.20 MPa.

Polyurethane foam including the airgel composite according to the present invention is coated with the airgel using polyurea, and by preventing the problem of polymer penetration into the airgel nanopores occurring in the existing composite foaming agent, the high thermal insulation airgel composite There is an advantage that can improve the insulation performance of polyurethane foam.

Comparing the above Examples and Comparative Examples, the thermal conductivity of the polyurethane foam comprising the airgel composite according to Examples 2 and 3 is 0.0215, whereas the thermal conductivity of the polyurethane foam according to the comparative example is 0.02223 W/mK, respectively. W / mK, decreased to 0.0207 W / mK, it was found that the thermal performance of the polyurethane foam containing the airgel composite was improved.

In addition, the conventional silica airgel has a problem in that mechanical properties are lowered due to the low bonding force between the inorganic silica airgel and the organic polyurethane. There was no difference in foam and mechanical strength. It can be seen that since the surface of the airgel composite is coated with polyurea, which is an organic material, mechanical properties are not deteriorated.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and may be manufactured in a variety of different forms, and those of ordinary skill in the art to which the present invention pertains will appreciate the technical spirit of the present invention. However, it will be understood that the invention may be embodied in other specific forms without changing essential features. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (22)

a) providing an airgel having a plurality of pores formed therein;
b) when the airgel is heated, modifying the surface of the airgel to be hydrophilic;
c) filling the pores with the liquid by immersing the hydrophilic modified airgel in a hydrophilic liquid; and
d) reacting the hydrophilic liquid on the surface of the airgel or the airgel, in which the pores are filled with the liquid, with an isocyanate-based compound, and coating the surface of the airgel with polyurea. A method of manufacturing an airgel composite. According to claim 1,
The step b) is a method of manufacturing an airgel composite that is performed in a temperature atmosphere of 300 ℃ to 500 ℃. According to claim 1,
After step d), the method of manufacturing an airgel composite further comprising the step of drying the airgel for 48 hours to 72 hours in a temperature atmosphere of 120 ℃ to 200 ℃. 4. The method of claim 3,
A method of manufacturing an airgel composite in which the liquid filled in the pores is removed. According to claim 1,
The airgel is a method of manufacturing an airgel composite formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide. According to claim 1,
The isocyanate-based compound is polymeric methylene diphenyl diisocyanate (PMDI), monomer methylene diphenyl diisocyanate (MMDI), toluene diisocyanate, torilene diisocyanate (torilene) diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI) and hexamethylene diisocyanate (HMDI) any one selected from the group consisting of a method of manufacturing an airgel composite. According to claim 1,
The hydrophilic liquid is water (water), methanol (methanol), ethanol (ethanol), isopropanol (isopropanol), diol, triol, diamine, triamines or a method of producing an airgel complex comprising a mixture of two or more thereof. Airgel having a plurality of pores; and
Including polyurea coated on the surface of the airgel,
The polyurea is an airgel composite that is not coated on the pores of the airgel. delete 9. The method of claim 8,
The airgel is an airgel composite formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide. In the polyurethane foam composition with improved thermal insulation,
polyol mixtures;
isocyanate-based compounds; and
An airgel having a plurality of pores formed therein, and an airgel composite composed of polyurea coating the surface of the airgel,
The polyurea is a polyurethane foam composition that is not coated in the pores of the airgel. delete 12. The method of claim 11,
The polyol mixture is a polyurethane foam composition comprising a polyether polyol and a polyester polyol. delete 14. The method of claim 13,
The polyether polyol is polyethylene glycol, polypropylene glycol, polyoxypropylene triol glycol or polytetramethylene glycol polyurethane foam composition. 14. The method of claim 13,
The polyester polyol is diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1 ,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 ,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2-n- At least one selected from the group consisting of butyl-2-ethyl-1,3-propanediol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naphthylene dicarboxylic acid A polyurethane foam composition. 12. The method of claim 11,
The isocyanate-based compound is, polymeric methylene diphenyl diisocyanate (PMDI), monomer methylene diphenyl diisocyanate (monomer methylene diphenyl diisocyanate, MMDI), toluene diisocyanate (toluene diisocyanate), torylene diisocyanate ( torilene diisocyanate, TDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), isoprone diisocyanate (IPDI), and hexamethylene diisocyanate (HMDI) any one selected from the group consisting of polyurethane foam composition. 12. The method of claim 11,
The airgel is a polyurethane foam composition formed of any one selected from the group consisting of silica, zirconia, titania, ceria, alumina, iron oxide, vanadia, antimony oxide and tin oxide. 12. The method of claim 11,
A blowing agent is further included, wherein the blowing agent is water, cyclopentane, carbon dioxide, hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroolefin (HFO) or methane dichloride. Polyurethane foam composition. 20. The method of claim 19,
Polyurethane foam composition further comprising an additive. 21. The method of claim 20,
The additive is at least one selected from the group consisting of a foaming catalyst, a gelling catalyst and a surfactant, a polyurethane foam composition. The polyurethane foam comprising the cured product of any one of claims 11, 13, 15 to 21, any one of the polyurethane foam compositions.

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